Batavia dammar resin coating compositions



metal objects and baked at a temperature of about 135 C. for about one-half hour. The product is a transparent, resistant coating.

Eample 8 Parts Melamine-formaldehyde resin F 25 Batavia dammar 75 4A composition containing these. ingredients is Example 9 Parts Melamine-formaldehyde resin F 75 Batavia dammar 25 A composition containing these ingredients is prepared by admixing 150 parts of melamineformaldehyde resin F solution (50% resin) with 100 parts of Batavia dammar stock solution.v Films of the composition are applied to metal objects and baked at a temperature of 'about 135 C. for about one-half hour. A hard,

transparent nlm is produced.

Example 10 Parts Melamine-formaldehyde resin G 50 Batavia dammar 50 A composition containing these ingredients is prepared by admixing 100 parts of melamineformaldehyde resin G" solution (50% resin) with 200 parts of Batavia dammar stock solution. Films of the composition are applied to metal objects and baked at a temperature of labout 135 C. for about one-half hour, to give a smooth,r transparent surface.

Preparation of melamine-formaldehyde resin "A" v Parts Melamine (1' mol) 126 Formalin (Il mols) (37% formaldehyde in Water) L 324.4 n-Butanol 440 This mixture is placed in a reflux apparatus which is provided with a condenser and a suitable Water trap through which the reflux condensate passes on its return to the reaction chamber and in which the essentially aqueous fraction of the condensate may be separated from the essentially non-aqueous fraction and means is provided s'o that the former fraction may be drawn off if desirable. The reaction mixture is refiuxe'd at a temperature of about 91-93" C. atatmospheric pressure for 6-12 hours.Y The Water is removed by azeotropic distillation from the reaction mixture during the reux operation beginning preferably after about 2-5 hours have elapsed and the Water so removed is separated from the reflux condensate -in the water trap. During the distillation about 550 additional parts of butanol are added gradually. When the reilux condensate is substantially anhydrous the vapor temperature will be about 10U-105 C. The .pressure is lowered. sufficiently to reduce the vapor temdiluted to about 50% solids with any "desiredsolvent or diluent, e. g., xylene.

Preparation of melamine-formaldehyde resin "B Parts Melamine (1 mol) 126 Formalin (5 mols) (37% formaldehyde in water) 405.5

n-Butanol 440 This mixture is placed in a reflux apparatus which is provided with a condenser and a suitable water trap through which the reilux condensate passes on its return to the reaction chamber and in which the essentially aqueous fraction of the condensate may be separated from the essentially non-aqueous fraction and means is provided so that the former fraction may be drawn off if desirable. The reaction mixture' is reiluxed at a temperature of about 91-93" C. at atmospheric pressure for 6-12 hours. The Water is removed by azeotropic distillation from the reaction mixture during the reflux operation beginning preferably after about 2-5 hours have elapsed and the Water so removed is separated from the reflux condensate in the Water trap. During the distillation about 550 additional parts of butanol are added gradually. When the' reflux condensate is substantially anhydrous the vapor temperature will -be about 10G-105 C. The pressure is lowered suicently to reduce the vapor temperature to about 85-90 C. and the resin solution is concentratedto about (S0-70% solids by vacuum distillation.` The resulting resin solution may be diluted to about solids with any desired solvent or diluent, e. g.,.xylene.

Preparation of melamine-formaldehyde resin C Parts Melamine (l mol) 126 Formalin (6 mols) (37% formaldehyde vin water) 486.6 n-Butanol 440 This mixture is placed in a reux apparatus which is provided with a condenser and a suitable water trap through which the reflux condensate passes on its return to the reaction chamber and in which the essentially aqueous fraction of the condensate may be separated from the essentially non-aqueous fraction and means is provided so that the former fraction may be drawn oi if desirable. The reaction mixture is refluxed at a temperature of about 91-93" C. at atmospheric pressure for 6-12 hours. The Water is removed by azeotropic distillation from the reaction mixture during the reflux 'operation beginning preferably after about 2-5 hours have elapsed and the Water so removed is separated from the reflux condensate in the Water trap. During the distillation about 550 additional parts of butanol are added gradually'. When the reux condensate is substantially anhydrous the vapor temperature will be about 10U-105 C. The pressure is lowered suiciently to reduce the vapor temperature to about 85-90" C. and the'resin solution is concentrated to about -70% solids by vacuum distillation. The resulting resin solution maybe diluted to about 50% solidc with anydesired solvent or diluent, e'. g., xylene. f

Preparation of melamine-formaldehyde resin "D" Parts Melamine-formaldehyde (molalv ratio 1:4)

spray-dried powder 300 n-Propanol 1200 Methyl acid phosphate 3 The melamine-formaldehyde condensation prodzata-asis@ uctisfdbtainedby refluxing-melamineand ciforma'- lin (37% formaldehydeiniwater) intheimolal ratio-fof 11:4 at a ip'H* of about 'l79 Zfor about 3 'hours-andSthen-spray-drying. l

The spray-dried#melaminelformaldehyde powder, :propan'ol andmethyl acid Yphosphate are `heatedtoabout -90 C` in Llil-'minutes andfrefluxed aboutv minutes. This `'solutionfis vacuum concentrated' at'fabout -5ft-60 1uIitilf'loFl parts of :volatilematerial arerdistilledfoff. The resinfsolution thus formed l contains about 48% fsolils.

Preparation-\offmelamieeformdldehyde:resin E "Parts Melamine '283 Formali'n- (37 `formaldehydein water) 978 This lmixture is Sheat'ed `Sat :about L.7G-143094()iuntil a lhomogeneous solution lis lobtained.. The :p'H :is adjusted-to about` 17.23 with '.causti'c'iand vacuum fconcentratedtoirem'oveabout `50-;7.0%iof1the yfree lwater. suiiicientffphosphoric acid his -zadded `to ne'utralizefthe .-'caustic-presentfand thenLBZO parts 'of #methanol -are added. 1W etfmethanol is `gradually distilled oii `from the mixturefand jdry methanol is addedl at about the sameiirateas wet methanol `is -dli'stilled Lofi. 2This distillation sand i-acitiit-ion#ofmethanolis continued until thedistilllatelis substantially dryfmethonaL vDuring this operation which #requires labout'lel fhou'rs, about 11600 parts fo'f fme'thano'l {are-added. 17.07 fparts of Pentasol (trade name ofviSharpl'esfSolvents Corporation for mixed :amm-alcohols) 'are @added and-'italie `distillation is continued until the vapor temperature rises, 'to about 150G-"105" vC.- YAbout zF parts ofithedistillatfeiare collected. The pressure is *lowered suiiicientl-yftoL'reduceL thetemperature j'to' 80%90" `"'C'. handfl-'dparts more fof i the dist'illate'arej collected; Avleaving 'as a product Y"a I'resin solution :containing l59% of 4resin *solids in ;Prrepamtonfof:melaminefonmaldehyde'resin fF Melamine v.(.1,.mol). l V "1'26 Forlrlalii'iH (5 111015) v(37% formaldehyde in waterl 405.5 n-Hexyl i alcohol- Methyl'alcohol rI'his mixture lis placed in a reflux apparatus which is provided with a condenser and a suit` able Water trap throughr which the reilux condensate passes on its return to the reaction chamber and in which the essentially aqueous fraction of the condensate maybe separated from the essentially non-aqueous fraction and means is provided so that the former fraction maybe drawn 01T if desirable. The reaction mixture is refluxed at a temperature of about 80-85 C. at atmospheric pressure for 6-12 hours. The water is removed by azeotropic distillation from the reaction mixture during the reiiux operation beginning preferably after about 2-5 hours have elapsed and A the water so removed is separated from the reux condensate in theA Water trap. When the reflux condensate is substantially anhydrous the vapor temperature will be about 1D0-105 Cf. The pressure is lowered suflioiently to reduce the vapor temperature to about 85-90 C. and theresin solution is concentrated to about 60-70% solids by vacuum distillation. This solution is essentially a hexylated resin in hexyl alcohol, all or nearly all of the methanol having been eliminated from it during the distillation. The resulting resin sol action .finayfbe diluted a@V about; 50% soucis with 'any desired-solventforf-diluent; .e.1g.; xylene.v iraparato@pfmiqaae-fbmamehyde msm Melamine formaldehyde '(mol'al ratio l' 1 :4)

sprayfdried2powden i 200 l'2:ethyl` hexanol 1 1280 =n-Butanol A f .320 Methyl acid-phosphate "4 Thegmiamine idrmidenydg condensation vprod- Vucjtjis dbtaine'dlby'frefluxingmelamine and forma- 1inY 'Trate/z. "fforir'iaidehyueiniwateri ,inthe mo1a1 ratio of 1;4 atlajpH'ofabout'-Qfforabout'3 hours and thenlspr'ay-drying; l

j spray? iieidfmenminafomaidenyde powwith vthe vhigher aldhols, e.,1g.',tl`ief,amyl alcohols, `hexyl alcoholsland the.oct'ano'ls,4 alow boiling alcohol `such vas".'metlianol 'or 'butanoll rI'nay be mixed With'the .octan'oLy thereby assisting inl removing tlie' Water A'and causing .the reactionlto' take v.place readily y atl smewhatlower Vtemperatures than i Wouldothervvise be required. Thelow boiling'alv'Parts rcoholis removed "bydistillation after the reaction isy completed/' Another' vmethod for producing resins alkylated 'wi'thoctanols is to alkylate the melamine-formaldehyderesin with `a lovvboiling :alcohol 'such as 'methanol and subsequently lneplaci'ng it Withthe desired octanol, ,distillingfout the loWv boiling alcohol. The condensation'may be carried out'either With'or withoutan acid'catalyst and in some v.instances 'basic catalysts may desirablyib'ejutilizedl p The'melamine-formaldehyde re'sinsvary 'slight- 'ly 'according to' minor lvariations of control Aduring their production and in some instances small proportions of a suitable solvent material, e. g., benzene, xylene, toluene, carbon tetrachloride, amyl acetate, etc., may be added to the original solutions of Batavia dammar resin and melamineformaldehyde resin in order to produce perfectly clear solutions if such solutions are not originally y,

obtained.

While formaldehyde has been used in the previous examples,y it will be obvious that other aldehydes such as various polymers of formaldehyde, e. g., paraformaldehyde, or substances which yield formaldehyde may be used in place of part or all .of the formaldehyde.

Melamine resins suitable for use according to our invention may be alkylated with acyclic straight and branched chain aliphatic alcohols containing at least 4 `carbon atoms. Obviously various mixtures of alcohols may be used. The term alkylated melamine-formaldehyde resin is intended to denote compositions which are reacted With an alcohol.

Insome instances melamine-formaldehyde resins alkylated with other alcohols have been found to be compatible with Batavia dammar resin in certain proportions. For example, up to about 25% of benzylated melamine-formaldehyde resins wherein the molal ratio of formaldehyde to melamine is about 5:1' are compatible with Batavia dammar resin. On the other hand, propylated melamine-formaldehyde resins wherein the molal ratio of formaldehyde to melamine is at least Yabout 4:1 are compatible with at least about 50% of the Batavia dammar resin. At least about 75% of a melamine-formaldehyde resin alkylated with ethylene chlorohydrin Wherein the molal ratio of formaldehyde to melamine is about 5.5: 1 is compatible with Batavia dammar resin. Furthermore, about of butylated melamine-formaldehyde resin wherein the molal ra'- tio of formaldehyde to melamine is about 3:1 is compatible with Batavia dammar resin. Higher proportions of this same melamine resin up to 90% are partially compatible with Batavia dammar resin. While higher ratios of formaldehyde to melamine than 6:1 may be used, it is generally undesirable inasmuch as formaldehyde is lost during the curingso that usually the product in its cured condition does not contain more than about 6 mois of formaldehyde to 1 mol of melamine, The percentage composition in each instance in this paragraph is on a total solids weight basis.

Our compositions may be used in admixture with other resinous compositions, e. g., ureaformaldehyde resins, phenol-formaldehyde resins, ester gum, chlorinated rubbers, alkyd resins, modiiied alkyd resinsl such as the terpene-maleic acid-polyhydric alcohol resins, etc. They may also be used in drying oil vehicles such as linseed oil and the like, especially in combination with soluble phenol-formaldehyde resin materials.

A wide variety of plasticizers may be incorporated into our products such as the alkyl phthalatevs, tricresyl phosphate, alkyd resins, etc.

Various fillers, pigments, dyes and lakes may be added to our compositions, e. g., lithopone, zinc oxide, titanium oxide, ferric oxide, Prussian blue, toluidine red, malachite green, mica, ground glass, glass bers, powdered silica, etc.

Curing catalysts maybe incorporated into the compositions to effect a more rapid curing of the melamine-formaldehyde resins or to enable the resin to be cured at lower temperatures than indicated in the above examples. Such substances are, for instance, vphosphoric acid, ammonium salts of phosphoric acid, etc.

Our compositions containing lmelamine-formaldehyde resin and Batavia dammar resin are especially useful in coating compositions which must meet high specifications for alkali resistance, water` resistance, etc. They also are quite tough and the original solutions have a high tolerance for hydrocarbons. Our compositions are especially useful in varnishes, lacquers, paints, enamels, etc., as well as in adhesives, in the production of printing inks, in treating paper and cloth, etc. Thev melamine-formaldehyde resins impart chemical resistance tothe compositions whereas the Batavia dammar resin provides increased toughness, hydrocarbon tolerance, adhesive properties, etc.

The term compatible as used herein is intended to denote compositions, films of which are clear and homogeneous after baking.

Obviously many modications and variations in the processes and compositions described above may be made without departing from the spirit and scope of the invention as deiined in the appended claims.

We claim:

1. A coating composition containing Batavia dammar resin and a melamine-formaldehyde resin which has been reacted with an aliphatic acyclic alcohol containing at least 4 carbon atoms and wherein the molal ratio of formaldehyde to melamine is at least about 4:1.

2. A coating composition containing Batavia dammar resin and a melamine-formaldehyde r resin which has been reacted with n-butanol and wherein the molal ratio of formaldehyde to melamine is at least about 4: 1.

' 3. A coating composition containing Batavia dammar resin and a melamine-formaldehyde resin which has been reacted with n-hexanol and wherein the molal ratio of formaldehyde to melamine is at least about 4:1.

4. A coating composition containing Batavia dammar resin and a melamine-formaldehyde resin which has been reacted with 2ethyl hexanol and wherein the molal-ratio of formaldehyde to melamine is at least about 4:1.

ROBERT C. SWAIN. PIERRllPOIVl1 ADAMS. 

